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. 2008 Mar 25;9(1):013007. doi: 10.1088/1468-6996/9/1/013007

Advances in principal factors influencing carbon dioxide adsorption on zeolites

Danielle Bonenfant 1, Mourad Kharoune 1, Patrick Niquette 1, Murielle Mimeault 2, Robert Hausler 1,✉
PMCID: PMC5099794  PMID: 27877925

Abstract

We report the advances in the principal structural and experimental factors that might influence the carbon dioxide (CO2) adsorption on natural and synthetic zeolites. The CO2 adsorption is principally govern by the inclusion of exchangeable cations (countercations) within the cavities of zeolites, which induce basicity and an electric field, two key parameters for CO2 adsorption. More specifically, these two parameters vary with diverse factors including the nature, distribution and number of exchangeable cations. The structure of framework also determines CO2 adsorption on zeolites by influencing the basicity and electric field in their cavities. In fact, the basicity and electric field usually vary inversely with the Si/Al ratio. Furthermore, the CO2 adsorption might be limited by the size of pores within zeolites and by the carbonates formation during the CO2 chemisorption. The polarity of molecules adsorbed on zeolites represents a very important factor that influences their interaction with the electric field. The adsorbates that have the most great quadrupole moment such as the CO2, might interact strongly with the electric field of zeolites and this favors their adsorption. The pressure, temperature and presence of water seem to be the most important experimental conditions that influence the adsorption of CO2. The CO2 adsorption increases with the gas phase pressure and decreases with the rise of temperature. The presence of water significantly decreases adsorption capacity of cationic zeolites by decreasing strength and heterogeneity of the electric field and by favoring the formation of bicarbonates. The optimization of the zeolites structural characteristics and the experimental conditions might enhance substantially their CO2 adsorption capacity and thereby might give rise to the excellent adsorbents that may be used to capturing the industrial emissions of CO2.

Keywords: zeolites, chemisorption, physical adsorption, carbon dioxide, surface structure

Introduction

The increased use of fossil fuels during the past 200 years contributes to the steady rise of CO2 level in the atmosphere, a major green house gas that contributes significantly to global warming [1, 2]. Several technologies to separate and capture the industrial emissions of CO2 have been developed. Among them, certain technologies are based on the CO2 adsorption/desorption by using natural and synthetic zeolites [3, 4]. The zeolites are a subclass of tectosilicates that possess a framework formed by a three-dimensional assemblage of tetrahedra [SiO4] and [(AlO4)-]. This assemblage gives rise to diverse framework structures including those shown in figure 1. The packing of zeolite structure allows the formation of regular cavities joint by the channels, where the molecules with an appropriate size such as the gas as CO2, water and the metallic exchangeable cations (Li+, Na+, K+, Ca2+, Ba2+, Cu2+, Zn2+, Mg2+, etc) can penetrate and compensate for the negative charges created by the substitution of AlO4 tetrahedron by SiO4 tetrahedron (figure 2) [6, 7]. The CO2 usually undergoes a physical adsorption (physisorption) and chemical adsorption (chemisorption) at the surface of zeolites. The zeolites are recognized to be the potent CO2 adsorbents that are able to adsorb and desorb CO2. The most of known zeolites have a capacity of CO2 adsorption at high pressures and low temperatures which varies from 0.15 to 5.5 mmol of CO2 (g of zeolite)−1 at 273–373 K (tables 1–3) [9–20]. The degree of irreversible adsorption of CO2 on zeolites M-ZSM-5 (M=Li+, Na+, K+, Rb+, Cs+) which has been evaluated under a pressure inferior to 6.7×10−2 MPa, was less than 10% of the total adsorption [21]. The adsorption capacity of zeolites depends on several factors including the size, polarizing power, distribution and the number of cations in their porous structure, Si/Al ratio, size, the form of their pores, the polarity and size of adsorbed molecules, the presence of water and other gas and presence of carbonates at their surface. Experimental conditions such as pressure and temperature are also among the factors influencing the adsorption capacity of zeolites.

Figure 1.

Figure 1

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Scheme showing the portions of the framework structures of (a) zeolite A, (b) faujasite (type X, Y) and (c) zeolite ZSM-5 (reprinted from [5] with permission from Trans Tech Publications).

Figure 2.

Figure 2

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Schematic diagram of zeolite 4A showing the sodium cations within cavities. The atoms of silicon, aluminum, oxygen and sodium in zeolite 4A are indicated in yellow, purple, red and green, respectively (reprinted with permission from [8] © 2004 American Chemical Society).

Table 1.

Effect of Si/Al ratio, temperature and pressure on CO2 adsorption capacity of the zeolite H-ZSM-5.

Adsorption
Temperature Pressure capacity
Zeolite Si/Al (K) (kPa) (mmol g−1) Reference
H-ZSM-5 15 281 81.63 2.148 [10]
15 293 91.02 2.114 [10]
15 309 88.75 1.869 [10]
30 281 84.58 1.902 [10]
30 293 94.94 1.832 [10]
30 309 92.33 1.602 [10]
60 281 52.54 1.375 [10]
60 293 81.44 1.377 [10]
60 309 84.67 1.279 [10]
280 313.15 101.3 1.24 [11]
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Table 3.

Effect of temperature and pressure on CO2 adsorption capacity of diverse zeolites.

Adsorption
Temperature Pressure capacity
Zeolite type (K) (kPa) (mmol g−1) Reference
13X and NaX 298.15 2068 5.2 [13]
293 0.55 1.07 [14]
273.15 102 4 [14]
293.15 102 3.4 [14]
313.15 102 2.75 [14]
333.15 102 2.3 [14]
353.15 102 2.0 [14]
303 2000 5.5 [15]
313 2000 5.0 [15]
323 2000 4.8 [15]
304.55 28.5 5.416 [16]
305.95 68.73 4.618 [16]
303 46.93 5.04 [17]
5A 303 120 3.068 [18]
303 1000 3.551 [18]
373 120 2.121 [18]
373 1000 3.168 [16]
373 120 0.239 [18]
573 1000 1.039 [16]
Na-ZSM-5 297.25 71.52 1.908 [16]
303 200 1.209 [19]
333 200 1.438 [19]
Li- ZSM-5 303 200 1.418 [19]
333 200 1.376 [19]
Cs-ZSM-5 303 200 1.334 [19]
333 200 1.251 [19]
Rb-ZSM-5 303 200 1.334 [19]
333 200 1.543 [19]
K-ZSM-5 303 200 1.209 [19]
333 200 1.501 [19]
MCM-41 323.15 101.3 0.325 [20]
348.15 101.3 0.195 [20]
373.15 101.3 0.150 [20]
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In this study, we report an advanced analysis of the most important factors influencing CO2 adsorption on natural and synthetic zeolites. The objective of this study is to enhance the understanding of the mechanism for CO2 adsorption on zeolites and provide data that could be used to evaluate the potential of their industrial application.

Theory

Influence of the structural characteristics of zeolites on the CO2 adsorption

Influence of the basicity

The basic properties of zeolites brought by cations allow a strong capitation of acidic molecules by enhancing the electron density of the framework oxygen [22, 23]. The basic strength of these sites increases with the electropositivity of exchangeable cations [24]. More specifically, certain works have indicated that the basic strength of cationic zeolites containing the cations of Group 1A increases as following: Li+<Na+<K+<Rb+<Cs+ [25, 26]. Study of CO2 adsorption on three zeolites, including natural hershelite-sodium chabazite (sodium aluminosilicate), clinoptilolite (sodium aluminosilicate) and clinoptilolite (potassium calcium sodium aluminosilicate), have also revealed that the capacities and rate of CO2 adsorption of natural hershelite-sodium chabazite and clinoptilolite (sodium aluminosilicate) are greater than clinoptilolite (potassium calcium sodium aluminosilicate) [27]. This difference of adsorption has been attributed to the higher basicity of the surface of natural hershelite-sodium chabazite and clinoptilolite (sodium aluminosilicate) as compared to that of clinoptilolite (potassium calcium sodium aluminosilicate), resulting from a greater amount of sodium ions on the natural hershelite-sodium chabazite and clinoptilolite (sodium aluminosilicate). Moreover, it has also been reported that the basicity of oxygen atoms of framework of zeolites NaX and NaY is strongly decreased by the substitution of Na+ cations by the Ba2+ cations [22]. This phenomenon might be caused by a decrease of partial negative charge of oxygen atoms adjacent to Ba2+ cations. In this matter, an analysis of the CO2 adsorption on zeolites KX, BaX and LaX has effectively indicated that the zeolite KX was the most basic among these three zeolites [28]. In contrast, a study of CO2 adsorption on the clinoptilolite has indicated that the substitution of Na+ and K+ by Ca2+ caused a rise of the basicity of the framework oxygen acting as basic center [7]. The basic strength and the capacity of CO2 adsorption of zeolites might also be increased significantly by occlusion of alkali metal oxides. The basic sites of basic metal oxides such as rare earth oxides and alkaline earth oxides, are considered to be more strongly basic that those of ion-exchanged zeolites [26]. In this matter, it has been observed that the occlusion of oxides of cesium (CsOx) in the zeolites NaX and NaY caused a rise of the basicity and capacity of CO2 adsorption on these zeolites, and the increase of the capacity of CO2 adsorption was proportional to amount of occluded CsOx [29].

Influence of the polarizing power, distribution, size and number of exchangeable cations

The adsorption of gas by the zeolites is also determined by the polarizing power of the exchangeable cations and their distribution, size and number that influence the local electric field and the polarization of adsorbed molecules on the zeolites [12]. In general, the polarizing power of the cations is inversely proportional to its ionic radius [30]. For instance, the diameters of cations from Group 1A vary as following: Cs+ (3.3 Å) >Rb+ (2.9 Å) > K+ (2.7 Å) > Na+ (1.9 Å) > Li+ (1.4 Å) and their polarity: Li+ > Na+ > K+ > Rb+ > Cs+ [31, 32]. Hence, the zeolites such as ZSM-5 and M-ZSM-5 (M=Li+, Na+, K+, Rb+, Cs+) which have small cations might penetrate more easily within channels, are able to interact more strongly with the CO2 [19, 33]. This is in agreement with the results from a study performed by Yamazaki et al. [21]. They showed that energy of the interaction between the CO2 and the cations sites of zeolites M-ZSM-5 (M=Li+, Na+, K+, Rb+, Cs+) decreases with the increase of the size of these cations sites. In parallel, the distribution of exchangeable cations in the different sites of the zeolites structure causes the heterogeneous character of the CO2 adsorption [17]. For example, it has been established for faugasite-type zeolites that molecules of CO2 might be adsorbed only in the supercage, and more specifically in sites localized within sodalite cage and/or in the hexagonal prism [22, 34, 35]. The position of extraframework cations sites in faujasite-type structure are shown in figure 3. In the case of zeolite NaX, the sodium ions that are accessible to CO2 molecules are localized in two sites: the sites II that are strongly bound to zeolite lattice and the sites III that are less bound and responsible of heterogeneous character of CO2 adsorption [17]. In regard with this, Khelifa et al [34, 37] have notably observed a decrease of the CO2 adsorption affinity when Na+ cations of an x-type zeolite are exchanged by the M2+ cations (Mg2+, Sr2+, Zn2+, Cu2+). However, there is an increase of the CO2 adsorption affinity when the degree of Na+ exchange increases. Khelifa et al [17] have also shown that the CO2 adsorption on the zeolites X exchanged with Ni2+ and Cr3+ decreases as compared to that of zeolite NaX due to a decrease of the adsorbate-adsorbent interaction. This phenomenon has been associated with a depopulation of sites III and a decrease of electric field in the cavities of zeolite. Nevertheless, it has been showed that the substitution of Na+ cations by the M2+ and Cr3+ cations changes only the CO2 adsorption when the rate of exchange is superior to 40–50%[17, 37, 38]. A similar effect has also been observed by Khvoshchev and Zverev [39] on the isosteric heat of CO2 adsorption on the dehydrated faujasites (Mg, Ca)-X and (Mg, Ca)-Y following the substitution of a part of the Ca2+ ions by the Mg2+ ions. The decrease of heat of adsorption achieved during the substitution has been attributed to a greater screening of Mg2+ ions by the oxygen atoms electric field of zeolites as compared to that of Ca2+ ions. This might be caused by the penetration of Mg2+ ions deep within six-membered rings of the framework or to their localization principally outside the cavities of zeolites. Coughlan and Kilmartin [40] and Coughlan and McCann [41] have also showed a decrease of CO2 affinity after an introduction of trivalent cations (Fe3+, Y3+, Cr3+, Co3+ and Tl+) in the X, Y, A and L type zeolites. According to these authors, this effect could be generalized to all the polyvalent cations of transition metals [41]. The number of cations which are able to interact with adsorbates has also an importance in the adsorption process. Indeed, a measurement of the heat of CO2 adsorption in faujasites CaY and CaX has indicated that the isosteric heat of CO2 adsorption on the zeolite CaX is higher than that of CO2 on the zeolite CaY. This could be a consequence of a higher CO2 adsorption on zeolite CaX than on the zeolite CaY [39]. Moreover, this difference could also be due to a greater number of Ca2+ cations in the zeolite CaX which are able to interact directly with the adsorbed CO2 molecules, than in zeolite CaY.

Figure 3.

Figure 3

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Scheme of unit cell of faujasite-type (X and Y) zeolites showing cations sites (reprinted with permission from [36] © 2000American Chemical Society).

Influence of the Si/Al ratio

It has been shown that the adsorption capacity and selectivity of zeolites for the polar molecules increases when the Si/Al ratio decreases [10]. This effect is more important when the quadrupole moment of molecules is great. This phenomenon could be due to an increase of electric field in the zeolites pores induced by increasing number of charged sites present at the surface of zeolites. Moreover, the basicity of zeolites framework enhances with the content of Al3+ ions due to the presence of a greater amount of exchangeable cations [42]. Hence, at low pressure, the zeolites that possess the more small Si/Al ratios should have the best adsorption capacity and selectivity for the polar molecules such as CO2. This phenomenon might be explained by the fact that the polarity of adsorbed molecules plays a more important role in their adsorption when the electric field into the zeolites pores is great. This is supported by the results of Calleja et al [10] and Harlick and Tezel [11] that have indicated that the CO2 adsorption capacity of H-ZSM-5 vary from 1.869 to 1.279 mmol of CO2 g−1 (temperature =309 K; pressure =88.75 and 84.67 kPa) when the Si/Al ratio of zeolite enhances from 15 to 60, as well as 1.24 mmol of CO2 g−1 (temperature =313.15 K; pressure = 101.3 kPa) with a Si/Al ratio of 280 (table 1). A study of CO2 adsorption on the erionite (ZAPS), mordenite (ZNT) and clinoptilolite (ZN-19) has also indicated that the adsorption of CO2 is greater on erionite than on the mordenite and clinoptilolite while the erionites: 3⩽Si/Al⩽3.5, mordenites: 4.17⩽Si/Al⩽5.0 and for the clinoptilolites: 4.25⩽Si/Al⩽5.25 (table 2) [12, 43].

Table 2.

CO2 adsorption capacity of erionite, mordenite and clinoptilolite.

Adsorption
Temperature Pressure capacity
Zeolite (K) (kPa) (mmol g−1) Reference
Erionite (ZAPS) 290.15 26.67 3.0 [12]
Mordenite (ZNT) 290.15 26.67 1.8 [12]
Clinoptilolite 290.15 26.67 1.7 [12]
(ZN-19)
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Influence of the size of pores

The pores size ofzeolites is another factor that might influence the capacity and rate of CO2 adsorption. In fact, the size of pores must be appropriate to allow to the adsorbed molecules topenetrate within them. The relationship between the CO2 adsorption capacity of zeolites and the size of their poresdepends particularly of the pressure (loading). Indeed, at low pressures, the density of the adsorbate is highest in the smaller pores while that is higher in larger poresat high pressures [44]. At the low pressures, the adsorbed molecules have the tendency to occupy the positions where the adsorbate-adsorbate interactions are less than the adsorbate-pore interactions, corresponding to the energetically most favorable positions. At high pressures, the adsorbed molecules might occupy the central region of the pores and the increase of their packing leads to the greater density [44–46]. This is corroborated by the fact that the affinity of the zeolite NaA for CO2 is highest than that of zeolites NaX and NaY (affinity for the CO2: NaA > NaX > NaY) at low pressures. This might be due in part to small pore diameter of zeolite A [16, 47, 48]. This high affinity of zeolite NaA allows a better selectivity for CO2 in the presence of N2 and O2 than NaX and NaY. Moreover, since the CO2 can also interact with the pore wall of zeolites, the CO2 adsorption might be limited by the size of zeolites pores at high pressures because the CO2–CO2 interactions might prevent the adsorption of new molecules of CO2 into the pore wall sites that are thus occupied by other molecules of CO2 [12, 19, 21]. The shape of pores also seems to be important for the selective adsorption of CO2. Inui et al [49] have suggested from a study of the CO2 adsorption on the natural and synthetic zeolites (chabazite, clinoptilolite, clinoptilolite–smectite-Opal C.T., mordenite, ferrierite, mordenite–ferrierite–pielite, erionite, MS-5A,MS-4A, MS-13X, H-ZSM-5), which have different structures, that the zeolites having three-dimensional pore connection structure are more performing for the CO2 separation.

Influence of adsorbates characteristics

Influence of the polarity of adsorbates.

The affinity of zeolites for some gas is also attributable to the polarity of adsorbed molecules. The molecules that have a great permanent quadrupole moment might interact strongly with the gradient of the electric field induced by the zeolites cations [50]. The quadrupole moment of certain gas varies as following: CO2>CO>N2>H2>CH4≈Ar≈Kr [28]. Goj et al [51] have effectively showed that the zeolites ITQ-3 and ITQ-7 adsorb preferentially the CO2 to detriment of N2. This selectivity has been attributed to a strengthening of Coulombic interactions between the CO2 molecules versus N2 and the electric field of zeolites, which might be caused by the quadrupole moment of CO2 (−1.43×1013 cm2) that is three times greater than that of N2. Nevertheless, according to Calleja et al [10] and Katoh et al [19] the selectivity of zeolites M-ZSM-5 (M=Li+, Na+, K+, Rb+, Cs+) might be due to fact that all the CO2 molecules are adsorbed on the cations sites while N2 might interact with the wall of ZSM-5. It has also been observed that the zeolites 13X, M-ZSM-5 (M=Li+, Na+, K+, Rb+, Cs+), ZSM-5, KY, 4A, Na-4A, 5A, clinoptilolite and Na-mordenite, adsorb selectively the CO2 in the presence of N2, O2, He, CH4, H2, C2H4, C2H6, SF6 and Ar [16, 18, 19, 51–56].

Influence of the dimension of adsorbates

Adsorbed molecules dimension seems also to play an important role in their adsorption on the zeolites. Actually, the porosity of zeolites cavities is selective factor for the absorbed molecules. For example, the erionites, mordenites, clinoptilolites and chabazite can adsorb only the molecules which possess kinetic diameter with a maximum of 4.3, 3.9, 3.5–3.8 and 4.3 Å, respectively, indicating that the CO2 adsorption (diameter =3.3 Å) is not limited by this steric factor [12, 16, 43, 57]. Moreover, it has been showed by Aguilar-Armenta et al. [7] that the require period for reach the middle of the capacity of CO2, O2 or N2 adsorption on Na-clinoptilolite and Ca-clinoptilolite is proportional to diameter of the adsorbed molecules (CO2<O2<N2).

Influence of the carbonates formation on the CO2 adsorption

In the case of several cationic zeolites, the chemical adsorption of CO2 is accompanied by the formation of carbonates including very stable monodentate or unidentate carbonates and bidentate carbonates, at their surface, due to the interaction of CO2 with the oxygen bridging aluminum and silicon atoms [24, 35, 58–62]. Gallei and Stumpf [58] have described the formation of monodentate carbonate at the surface of zeolite CaY by a reaction involving three steps. In the first step, the CO2 is polarized following its interaction with the neighboring Ca2 + ions. After this, the atom of carbon of CO2 attacks the oxygen bridging aluminum and silicon atoms, and this results in the rupture of aluminum oxygen bond, and the formation a stable monodentate carbonate species at the surface of zeolite (figure 4) [58, 59]. The presence of these carbonates might decrease the accessibility of CO2 at a great part of the surface of zeolites and thereby contribute to limit its adsorption. This is notably the case of the unidentate surface carbonate species formed during the CO2 adsorption on zeolite CaY that makes inaccessible approximately 20% of the surface cations [59].

Figure 4.

Figure 4

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Scheme showing the formation of monodentate carbonate on CaY-zeolite (reprinted from [58] © 1976, with permission from Elsevier).

Influence of the presence of water on the CO2 adsorption

Brandani and Ruthven [63] have observed that small amounts of water can inhibited the CO2 adsorption on diverse cationic forms of zeolites X (NaLSX, LiLSX, CaX), notably for zeolites NaLSX at 35 and 70 ∘C. According to these authors, this can be due to a reduction of the strength and heterogeneity of the zeolites electric field caused by a high adsorption capacity of water on the exchangeable cations generated by its strong polarity. The presence of water during the CO2 adsorption on the zeolites surface seems also to favor the formation of bicarbonates species via hydroxyl group formation [27]. The bicarbonates causes an increase of the CO2 desorption temperature. As it is shown by Siriwardane et al [27], a strongly bound CO2 in bicarbonates or bidentate carbonate type species formed on a natural herschelite-sodium chabazite and two forms of clinoptilolites was desorbed at 115 °C, while the majority of the physically adsorbed CO2 was desorbed at room temperature.

Influence of the pressure and temperature on the CO2 adsorption

Several investigations carried out with diverse zeolites (LaM-10, H-ZSM-5, M-ZSM-5 (M = Li+, Na+, K+, Rb+, Cs+), NaX or 13X, 5A, 4A, NaLSX, MCM-48, erionite, mordenite, clinoptilolite) have shown the effect of pressure and temperature on CO2 adsorption [10–12, 14, 16, 18, 19, 37, 52, 63–67]. In general, the capacity of CO2 adsorption on the zeolites enhances when the partial CO2 pressure increases and decreases with a rise of temperature (table 3). The results obtained by Yucel and Ruthven [68] and Gardner et al [69] have also shown that the diffusion of CO2 in the zeolite 4A and H-ZSM-5 enhances with the increase of the partial pressure. Moreover, the data obtained by Akten et al [52] have indicated that the Na-4A selectivity for the CO2 in the presence of N2 and H2 decreases slightly when the pressure in the gas phase enhances. This decrease of selectivity is more marked when the molecules of other gas smaller than CO2 are presents in the gas phase. The effect of the pressure on the CO2 adsorption might be attributed to fact that the amounts of CO2 adsorbed are directly proportional to the cationic density in the zeolites pores at low pressures, whereas the volume of pores plays an important role at high pressures [9, 44]. Katoh et al [19] have also attributed this effect of the pressure in the case of the zeolite Li-ZSM-5, to the existence of two types of cations sites species and to the possibility that a rise of the partial pressure might induce a penetration of CO2 deep into the small channels of zeolite, this allowed to interact more strongly with the Li+ cations. In parallel, the decrease of the CO2 adsorption with the increase of the temperature has been associated with a decrease of adsorbent-adsorbate interactions (site–adsorbate) induced by an increase of the mobility of adsorbed molecules into the zeolites cavities that might be caused by a rise of thermal agitation [34].

Conclusions

Zeolites have a high potential for CO2 capture, reaching an adsorption efficiency of 5.5 mmol of CO2/g of zeolite, combined with a degree of irreversible adsorption inferior to 10% (tables 1–3) [9–21]. The CO2 adsorption is influenced by diverse structural characteristics of zeolites including size, polarizing power, distribution and the number of exchangeable cations in their cavities, the size of the pores and the Si/Al ratio. Moreover, the characteristics of adsorbates such as the size and the polarity, the formation of carbonates species at the surface of zeolites during the CO2 adsorption, the presence of water and the conditions of adsorption including the gas phase pressure and temperature may also influence the CO2 absorption. More specifically, the capacity of CO2 adsorption on zeolites depends firstly of the basicity and the strength of electric field induced by the presence of exchangeable cations in their cavities as well as the size both of their pores and the adsorbate molecules. Generally, the zeolites, which are very basic and possess a strong electropositivity, show a best capacity of adsorption for the molecules that have an acidic character and a great permanent quadrupole moment such as CO2. In fact, this permits to them to strongly interact with the gradient of the electric field of the zeolites. In this case the polarizing power of exchangeable cations represents a very important factor that influences the local electric field and the polarization of the CO2 molecules on the zeolites. Furthermore, the adsorption is also increased in the presence of small exchangeable cations that can penetrate more easily within the zeolites cavities, and thereby interact stronger with CO2 as the big cations. Additionally, the adsorption is also influenced by the number of molecules that are able to interact with CO2, and their distribution which is responsible of the heterogeneous character of the CO2 adsorption. The CO2 adsorption also depends of framework of the zeolites. More particularly, the adsorption capacity and selectivity for the CO2 are favorized on zeolites that possess the small Si/Al ratio due to an increase of number of charged sites and basicity at the surface which is caused by the substitution of Si4 + ions by the Al3 + ions. On the other hand, the formation of carbonate species at the surface of zeolites during the chemisorption of CO2 is a factor that can significantly limit the CO2 adsorption of by the blockade of surface cations. The presence of water can also decrease the CO2 adsorption capacity of different forms of cationic zeolites by decreasing the strength and the heterogeneity of the electric field. Moreover, the presence of water can support the bicarbonates formation on the zeolites surface and thus generate strongly bound CO2 (bicarbonate species), which requires a higher temperature for its desorption. Finally, the diffusion of CO2 in the zeolites generally enhances with the pressure, and this results in an increase of its adsorption. In contrast, the decrease of adsorbent–adsorbate (zeolite-CO2) interactions induced through the increase of the temperature is an unfavorable factor for its adsorption.

On the basis of this advanced analysis of the most important studies about the CO2 adsorption using natural and synthetic zeolites, it appears that the basicity and size of pores of zeolites, as well as the strength of electric field caused by the presence of exchangeable cations in their cavities are the essential factors for the CO2 adsorption on zeolites. Thus, the consideration of all these factors seems to be necessary for the best choice of an appropriate zeolite for CO2 adsorption. Hence, the optimization of all these factors and experimental conditions may increase significantly the zeolites adsorption capacities and thus develops efficient technologies to capture the industrial emissions of CO2.

Acknowledgment

This work was supported by the grants from Natural Sciences and Engineering Research Council of Canada (NSERC).

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